WO1998012253A1

WO1998012253A1 - Flame retardant composition

Info

Publication number: WO1998012253A1
Application number: PCT/SE1997/001561
Authority: WO
Inventors: Bernt-Åke SULTAN; Matti Hirvensalo; Jussi Laurell
Original assignee: Borealis AS
Current assignee: Borealis AS
Priority date: 1996-09-17
Filing date: 1997-09-16
Publication date: 1998-03-26
Anticipated expiration: 1999-03-17
Also published as: US6166120A; CA2265762A1; DE69717130T2; SE9603371L; BR9712049A; ATE227755T1; AU4406797A; ES2187817T3; SE9603371D0; JP2001500559A; EP0927224B1; DE69717130D1; EP0927224A1; CN1176989A; AU715219B2; SE507330C2; CN1196769C; KR20030029656A; KR100509213B1

Abstract

The present invention relates to a flame retardant composition comprising (A) a polymer which includes a copolymer of ethylene and at least one other comonomer including a vinyl unsaturated polybishydrocarbylsiloxane; and (B) an inorganic filler comprising at least one member selected from the group consisting of oxides, hydroxides and carbonates of aluminium, magnesium, calcium and barium. It also relates to a cable or wire comprising such a composition.

Description

FLAME RETARDANT COMPOSITION

The present invention relates to a flame retardant composition and to a cable or wire having a layer comprising such a flame retardant composition.

It is known to use flame retardant compositions con- taining halides.

It is also known to increase the flame retardancy of polymer compositions by incorporating into the compositions relatively large amounts, typically 50 to 60- by weight, of inorganic fillers which decompose endothermi- cally liberating an inert gas at a temperature in the range of 200 to 600°C. In the 1970s use of aluminium hydroxide Al{OK)₃ was prevalent. I the 1990s use of Mg(OH)₂ became more frequent. Also CaC0 has been used for the same purposes . Flame retardant additive systems which use silicone fluids have also been proposed for use in polyolefin compositions. For example EP 0 393 959 discloses a flame retardant polymer composition comprising (A) an organic polymer, at least 40% by weight of which is a copolymer of ethylene with one or more comonomers selected from the group consisting of Ci to C_ alkyl acrylates, C_ to Cs alkyl methacrylates, acrylic acid, methacrylic acid and vinyl acetate, (B) a silicone fluid or gum, and (C) an inorganic filler which is a compound of a metal of Group II A of the Periodic Table of Elements (on the inside cover of Perry et al "Chemical Engineers' Handbook" 5th edition 1973) , but which is neither a hydroxide nor a substantially hydrated compound.

A disadvantage with the flame retardant compositions containing halides is that on combustion they release halide containing compounds which are harmful to the environment.

A disadvantage with the known silicone containing compositions is that silicone gum is generally in the form of lumps, which are difficult to handle. In order to render it fluid it must be pre-heated and pumped. Further, admixed silicone gum has a tendency to migrate in the composition during extrusion, which may give rise to depositions, so-called die drool, on equipment such as dies used in the process. It also clogs the embossing wheels used for applying identification marks on cables. Besides, silicone gum constitutes an extra component, the handling of which entails longer processing times and higher costs.

According to the present invention the above mentioned disadvantages are alleviated or eliminated by a flame retardant composition comprising a copolymer which as a monomer includes a silicon-containing compound. Thus, instead of being mixed with the polymer of he flame retardant composition, the silicon-containing compound is polymerised into the polymer and forms an integral part thereof. Besides preventing die drool, this also results in a composition with fewer components than in the known compositions, and this constitutes yet another advantage and leads to a better homogeneity of the composition.

Another advantage with the composition according to the invention is the fact that less silicone compound is needed in the new composition compared to the known com- positions.

Thus, the present invention relates to a flame retardant composition comprising:

(A) a polymer which includes a copolymer of ethylene and at least one other comonomer including a vinyl un- saturated polybishydrocarbylsiloxane according to formula

(I) :

R' R'

I I H₂C=CH-(Si-0)_n-Si-R (I)

I I

R' R' wherein n = 1-1000, and R and R', independently, are vinyl; alkyl, branched or unbranched, with 1-10 carbon atoms; aryl with 6 or 10 carbon atoms; alkylaryl with 7- 10 carbon atoms; or arylalkyl with 7-10 carbon atoms (preferred due to its commercial availability is vinyl polydimethylsiloxane) ; and

(B) an inorganic filler comprising at least one member selected from the group consisting of oxides, hydroxides and carbonates of aluminium, magnesium, calcium and barium.

It also relates to manufactured items containing such a compositio and in particular to a cable or wire having a layer comprising such a flame retardant composition. The characterising features of the invention will be evident from the following description and the appended claims .

Despite the fact that the siloxane according to the invention is polymerised, and thus bonded, a surprisingly good Limiting Oxygen Index (LOI) value is achieved; it is considerably higher than fcr a composition not comprising any silicone and of the same magnitude as LOI values for compositions comprising similar amounts of silicone gum mixed with a polymer. The Limiting Oxygen Index (LOI), according to ISO 45Θ9-A-IV, is a measurement of a products flame resistance. To determine the LOI-value a test specimen of the compound to be evaluated is ignited in an atmosphere of a mixture of nitrogen and oxygen. The content of oxygen in the N₂/0₂ mixture is gradually decreased until the specimen stops burning. The percentage of 0₂ in that N₂/0₂ mixture constitutes the compound's LOI-value. A high LOI- value means that a high percentage of oxygen is needed to sustain combustion, i.e. the compound has a good flame resistance. The LOI-value for a flame retardant composition should be at least 22, and higher values are desirable. As indicated above, the polymer containing the vinyl unsaturated polybishydrocarbylsiloxane monomer of formula (I) is a copolymer of ethylene and the monomer of formula (I), optionally with one or more additional co- monomers. These additional comonomers are preferably selected from the group consisting of C_-C₅ alkyl acrylates, Ci-Cs alkyl methacrylates, acrylic acid, methacrylic acid, vinyl acetate, vinyl tri ethoxysilane and vinyl triethoxysilane. In this connection it should be noted that the term "copolymer" as used herein includes grafc copolymers in which one or more of the comonomers is grafted onto the polymer backbone.

The above polymer including the monomer of formula (I) preferably comprises at least 4C., more preferably at least 60% by weight of the polymer of the flame retardant composition.

In addition to the above defined ethylene copolymer the composition according to the present invention may also include other, admixed polyolefms such as, for example, homopolymers and copolymers cf ethylene, propylene and butene and polymers of butadiene or isoprene. Suitable homopolymers and copolymers of ethylene include low density polyethylene, linear low, medium or high density polyethylene, and very low density polyethylene. Other suitable polymers include polyesters, polyethers and polyurethanes. Elastomeric polymers may also be used such as, for example, ethylene-propylene rubber (EPR) , ethylene-propylene-diene monomer rubbers (EPDM) , thermo- plastic elastomer rubber (TPE) and acrylonitrile butadiene rubber (NBR) . Silane-crosslinkable polymers may also be used i.e. polymers prepared using unsaturated silane monomers having hydrolysable groups capable of crosslinking by hydrolysis and condensation to form silanol groups in the presence of water and, optionally, a silanol condensation catalyst. The silane-crosslinkable polymer can be for example a copolymer of ethylene and an unsaturated silane monomer, such as vinyl trialkoκy- silane, produced by copoly erising the monomers in a polymerisation reactor or by grafting the silane monomer onto a polyethylene backbone. The amount of vinyl polybishydrocarbylsiloxane in the composition according to the present invention is approximately 0,01-30% by weight, preferably 1-10% by weight and more preferably 3-7% by weight.

The inorganic fillers suitable for use in the flame retardant composition according to the present invention are oxides, hydroxides and carbonates of aluminium, magnesium, calcium and/or barium. Examples of suitable inorganic fillers are calcium carbonate, magnesium oxide and huntite MgCa (C0₃) 4. The amount of inorganic filler in the composition according to the invention is l.-7_ by weight, and preferably 15-45% by weight.

In addition to the polymer ar.d inorganic filler, the compositions according to the present invention may con- tain additional ingredients suc as, for example, anti- oxidants and small amounts of other conventional polymer additives .

Suitable amounts of the components in the flame retardant composition according to the invention are speci- fied above. However, it will be apparent to a person skilled in the art that the proportions to be used should be selected to give the required balance of properties, in particular to give balance between the flame retar- dancy and the physical properties of the composition. The flame retardant compositions according to the present invention are suitable for use in, for example, cables such as installation cables and flexible cables, pipes, tubes, hoses, electrical contacts etc.

The invention is further illustrated by the follow- ing example, which in no way should be construed to limit the scope of the invention. Examole

The flame retardant composition according to the present invention was compared to known flame retardant compositions. The compounds used in this example were mixed in a Brabender cokneader at lδO°C resulting in compounds comprising known compositions as well as a compound comprising the composition according to the invention and, finally, a compound containing no silicone. The evaluation of their LOI-values was performed, as described above, after milling the extrudate and moulding the resulting granulate into 3 mm thick sheets.

The compounds and the LOI-values are shown in table 1. Compound 1 comprises only calcium carbonate a.s a flame retardant substance and no silicone. Compound 2 and compound 3 both comprise a flame retardant composition according to the present invention. Compounds 4-6 comprise different known flame retardant compositions. The polymer in the flame retardant composition according to the invention in examples 2 and 3 was a ter- polymer of ethylene, vinyl unsaturated polydimethyl- siloxane and butyl acrylate.

The known flame retardant composition comprised mix- tures of silicone gum with an ethylene-ethyl acrylate copolymer and different inorganic flame retardant additives.

Table 1

[Component Componnrl 1 Compound 7 Compound i Compound 4 Compound 5 Compound 6

CaC0₃ ¹ 30' 30 % 30% Mg⁽0»⁾ ₂ ² 30?. 307. Mg(OH)₂ ³ 30'.'. E/Si/BΛ-ter- polymcr * G'J.U^' G').ϋ% Silicone gum EEA⁵ 69.0% G4.fr.', G4.0% G4.0% IB-215 (Irganox, stabiliser) 0.2% 0.2% 0.2% 0.21 0.2% 0.2% Density 1.17 (j/cm³ 1.17 g/cm³ 1.10 rj/cm¹ 1.18 g/cm³ 1.1 ^r:- g/cm³ LOI 20.0 3 .6 20.6 30. 35.2 37.0

¹ O ya EX-HI SP

² Kisuma 5J from Kyowa Chemicals

³ FR 20 MHRM 105 from Dead Sea Bromine

* Ethylene terpolymer containing 14% I3Λ and 3.6% vinyl polydimethylsiloxane; n in formula (I) is 100 ⁵ EEΛ = Ethylene/ethyl acrylate copolyinei: with 15.3% EΛ (tjrade OE5010 from Borealis)

The LOI-values obtained for the Compounds 2 and 3 according to the invention were markedly better than that of Compound 1 containing no silicone, but somewhat lower than those of the compounds containing a mixture EEA and silicone gum. It has to be remarked though that the total amount of siloxane in compounds 2 and 3 was 2.5%, i.e. only half of that in compounds 4-6, which contained 5% silicone gum. By increasing the siloxane content in the compositions according to the invention a higher LOI- value may be obtained.

Claims

1. A flame retardant composition comprising:

(A) a polymer which includes a copolymer of ethylene and at least one other comonomer including a vinyl un- saturated polybishydrocarbylsiloxane according to formula (I) :

R' R'

wherein n = 1-1000, and R and R', independently, are vinyl; alkyl, branched or unbranched with 1-10 carbon atoms; aryl with 6 or 10 carbon atoms; alkylaryl with 7- 10 carbon atoms; or arylalkyl with 7-10 carbon atoms; and

(B) an inorganic filler comprising at least one member selected from the group consisting of oxides, hydrox- ides and carbonates of aluminium, magnesium, calcium and barium.

2. A flame retardant composition according to claim

1, wherein the copolymer includes at least one further comonomer selected from the group consisting of C₁-C.5 alkyl acrylates, C₁-C₅ alkyl methacrylates, acrylic acid, methacrylic acid and vinyl acetate.

3. A flame retardant composition according to claim

2, wherein the copolymer including the vinyl unsaturated polybishydrocarbylsiloxane comonomer constitutes at least 40% by weight of the polymer part of the total composition.

4. A flame retardant composition according to any one of claim 1-3, wherein the amount of vinyl polybishydrocarbylsiloxane comonomer is approximately 0,01-30% based on the weight of the total composition.

5. A flame retardant composition according to any one of claim 1-4, wherein the amount of vinyl polybis- hydrocarbylsiloxane comonomer is approximately 1-10% based on the weight of the total composition.

6. A flame retardant composition according to any one of claim 1-5, wherein the amount of vinyl polybis- hydrocarbylsiloxane comonomer is 3-7% based on the weight of the total composition.

7. A flame retardant composition according to any one of claim 1-6, wherein the amount of inorganic filler is approximately 10-70% based on the weight of the total composition.

8. A flame retardant composition according to any of claim 1-7, wherein the amount of inorganic filler is approximately 15-45% based cn the weight of the total composition.

9. A flame retardant composition according to any one of claim 1-8, wherein the polymer includes a copolymer of ethylene, a vinyl unsaturated polydimethylsiloxane according to formula (I), and butyl acrylate.

10. A cable or wire having a layer comprising a flame retardant composition according to any one of claim 1-9.